Diglycidylbenzimidazolones

ABSTRACT

Substituted and/or fused diglycidylbenzimidazolones which can be used, by curing with amines or anhydrides, for the manufacture of carting resins, electrical resins, sintering powders and compression moulding compositions.

111 States Patent 119] [111 3, Porret Oct. 22, 1974D1GLYCIDYLBENZIMIDAZOLONES [58] Field of Search 260/3092 [75] Inventor:Daniel Porret, Binningen,

Switzerland [56] References Cited [73] Assignee: Ciba-Geigy Corporation,Ardsley, FOREIGN PATENTS OR APPLICATIONS N.Y. 1,191,544 9/1967 GreatBritain 260/309.5 1,511,346 12/1967 France 260/309.7 [22] Flled- 1972271,005 12/1970 U.S.S.R 260/3092 [2]] App]. No.: 319,268

Primary ExaminerNata1ie Trousof [30] Foreign Application Priority DataJan 5, 1972 Switzerland 1. 109/72 [57] ABSTRACT Substituted and/or fuseddiglycidylbenzimidazolones [52] US. Cl 2611/3092, 260/2 EP, 260/2 EC,which can be used, by curing with amines or anhy- 260/2 EA, 260/2 N,260/ 18 EP, 260/30.4 EP, drides, for the manufacture of carting resins,electrical 260/30.6 R, 260/3L8 E, 260/37 EP, resins, sintering powdersand compression moulding 260/78.4 EP, 260/824 EP, 260/830 R,compositions.

260/830 S, 260/830 TW 511 1111. c1 00711 49/38 1 Clam, DrawmgsDHGLYCTDYLBENZIMIDAZOLONES The subject of the invention are new,substituted and/or fused diglycidylbenzimidazolones which can be used,by curing with amines or anhydrides, for the manufacture of castingresins, electrical resins, sintering powders, compression mouldingcompositions, B- stages and the like.

Diglycidylimidazolidones based on ethyleneurea or propyleneurea arealready known from Swiss Patent Specification 471,149.

Further, diglycidylbenzimidazolone has been described in the RussianPatent Specification 271,005. There, attention is also drawn to theexceptional compressive strength of the cured resins.

The diglycidylbenzimidazolones according to the invention, which can bemanufactured easily and in high purity, lead to cured products which aremore stable to water. They correspond to the formula (I) wherein atleast one X from amongst X X X and X, denotes an alkyl group with l to 4carbon atoms or halogen or two adjacent X together represent a fusedbenzene radical and the remaining X denote hydrogen.

Preferably, one X denotes the methyl group and the remaining X denotehydrogen atoms, or X, and X together form a fused benzene ring.

The diglycidyl ethers of the formula (I) can be manufactured fromcompounds of the formula (ll) sodium carbonate or potassium carbonatecan also be used for the purpose.

A further radical Z which can be converted into the 1,2-epoxyethylradical is, for example, the ethylene radical which can be convertedinto the 1,2-epoxyethyl radical in a known manner, such as, above all,by reaction with hydrogen peroxide or per-acids, for example peracetic,perbenzoic or monoperphthalic acid.

The starting substances of the formula (ll) are obtained in a mannerwhich is in itself known. Thus, one mo] of a substituted or fusedbenzimidazolone is reacted with 2 mols of an epihalogenohydrin, aboveall epichlorohydrin, in the presence of a catalyst such as, inparticular, a tertiary amine, a quaternary ammonium base or a quaternaryammonium salt. Suitable catalysts for the addition of epichlorohydrinare above all tertiary amines, such as triethylamine, tri-n-propylamine,benzyldimethylamine, N,N'-dimethylaniline and triethanolamine;quaternary ammonium bases, such as benzyltrimethylammonium hydroxide;quaternary ammonium salts, such as tetramethylammonium chloride,tetraethylammonium chloride, benzyltrimethylammonium chloride,benzyltrimethylammonium acetate and methyltriethylammonium chloride;hydrazines with a tertiary nitrogen atom, such as l,l-dimethylhydrazine,which can also be employed in quaternised form; alkali halides such aslithium chloride, potassium chloride or sodium chloride, bromide orfluoride; also, ion exchange resins with tertiary or quaternary aminogroups as well as ion exchangers with acid amide groups. It is alsopossible to work without a catalyst.

The addition of the epihalogenohydrin to the substituted or fusedbenzimidazolone can be carried outwith or without solvent, with anexcess of epichlorohydrin, at temperatures up to 140C, under the actionof one of the catalysts mentioned, in 30 to 360 minutes. The subsequentdehydrohalogenation can be carried out at 40 to C with solid or liquidalkalis and optionally whilst azeotropically distilling off the waterformed. The alkali halide is separated off in a known manner. Theresulting diglycidyl derivatives are isolated by distilling off theexcess epihalogenohydrin and, if appropriate, the solvent. They are as arule obtained as crude crystals in yields of up to percent.

The substituted or fused benzimidazolones can be manufactured in a knownmanner by condensing appropriately substituted or fusedo-phenylenediamines with phosgene.

The diglycidyl compounds according to the invention of the formula (1)react with the customary curing agents for epoxide compounds. They cantherefore be crosslinked or cured by addition of such curing agents,analogously to other polyfunctional epoxide compounds. Basic or acidcompounds can be used as such curing agents.

As suitable curing agents there may, for example, be mentioned: aminesor amides, such as aliphatic, cycloaliphatic or aromatic, primary,secondary and tertiary amines, for example monoethanolamine,ethylenediamine, hexamethylenediamine, trimethylhexamethylenediamine,diethylenetriamine, triethylenetetramine, tetraethylenepentamine,N,N-dimethylpropylenediamine-l ,3, N,N-diethylpropylenediamine- 1,3,2,2-bis-(4'-aminocyclohexyl)propane, 3,5,5-trimethyl-3-(aminomethyl)-cyclohexylamine (isophoronediamine), Mannichbases, such as 2,4,6- tris-(dimethylaminomethyl)-phenol; m-

phenylenediamine, p-phenylenediamine, bis-(4- aminophenyl)-methane,bis-(4-aminophenyl)-sulphone and m-xylylenediamine; adducts ofacrylonitrile or monoepoxides, such as ethylene oxide or propyleneoxide, to polyalkylenepolyamines, such as diethylenetriamine oftriethylenetetramine; adducts of polyamines, such as diethylenetriamineor triethylenetetramine in excess, and polyepoxides, such asdiomethane-polyglycidyl-ethers; ketimines, for example from acetone ormethyl ethyl ketone and bis(paminophenyl)-methane; adducts ofmonophenols or polyphenols and polyamines; polyamides, especially thosefrom aliphatic polyamines, such as diethylenetriamine ortriethylenetetramine, and dimerised or trimerised unsaturated fattyacids, such as dimerised linseed oil fatty acid (VERSAMID); polymericpolysulphides (THIOKOL); dicyandiamide, anilineformaldehyde resins;polyhydric phenols, for example resorcinol,2,2-bis-(4-hydroxyphenyl)-propane or phenol-formaldehyde resins; borontrifluoride and its complexes with organic compounds, such as BF -ethercomplexes and BF -amine complexes, for example BF monoethylaminecomplex; acetoacetanilide-BF complex; phosphoric acid;triphenylphosphite; polybasic carboxylic acids and their anhydrides, forexample phthalic anhydride, N-tetrahydrophthalic anhydride,hexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride,3,6-endomethylene-A -tetrahydrophthalic anhydride,4-methyl-3,6-endomethylene-A -tetrahydrophthalic anhydride methylnadicanhydride), 3,4,5,6,7,7-hexachloro-3,6-endomethylene-A-tetrahydrophthalic anhydride, succinic anhydride, adipic anhydride,trimethyl adipic anhydride, azelaic anhydride, sebacic anhydride, maleicanhydride, dodecenylsuccinic anhydride; pyromellitic dianhydride ormixtures of such anhydrides.

Curing accelerators can furthermore be employed in the curing reaction,and in particular when using polyamides, dicyandiamide, polymericpolysulphides or polycarboxylic acid anhydrides as curing agents; suchaccelerators are, for example, tertiary amines, their salts orquaternary ammonium compounds, for example2,4,6-tris-(dimethylaminomethyl)phenol, benzyldimethylamine,2-ethyl-4-methyl-imidazole and triamylammonium phenolate; or alkalimetal alcoholates, such as, for example, sodium hexanetriolate.

A further subject of the invention are curable mixtures which contain adiglycidyl compound according to the invention, of the formula (I),optionally together with other polyepoxide compounds, and also curingagents for epoxide resins, such as polyamines or polycarboxylic acidanhydrides.

The diglycidyl compounds according to the invention or their mixtureswith other polyepoxide compounds and/or curing agents can be mixed,before curing, with customary modifiers, such as extenders, fillers andreinforcing agents, pigments, dyestuffs, plasticisers, flow controlagents, agents for conferring thixotropy, flameproofing substances andmould release agents.

As extenders, reinforcing agents, fillers and pigments which can beintroduced into the curable mixtures according to the invention theremay, for example, be mentioned: coal tar, bitumen, glass fibres, boronfibres, carbon fibres, cellulose, polyethylene powder, polypropylenepowder, mica, asbestos, quartz powder, slate powder, aluminium oxidetrihydrate, chalk powder, gypsum, antimony trioxide, bentones, silicaaerogel (AEROSlL), lithopone, baryte, titanium dioxide, carbon black,graphite, iron oxide or metal powders, such as aluminium powder or ironpowder.

Suitable organic solvents for modifying the curable mixtures are, forexample, toluene, xylene, n-propanol,

butyl acetate, acetone, methyl ethyl ketone, diacetone alcohol, ethyleneglycol monomethyl ether, monoethyl ether and monobutyl ether.

Particularly for use in the lacquer field, the new diglycidyl compoundscan furthermore be partially or completely esterified in a known mannerwith carboxylic acids such as, in particular, higher unsaturated fattyacids. It is furthermore possible to add other curable synthetic resins,for example phenoplasts or aminoplasts, to such lacquer resinformulations.

The curable mixtures can serve, in the unfilled or filled state,optionally in the form of solutions or emulsions, as laminating resins,paints, lacquers, dipping resins, impregnating resins, casting resins,compression moulding compositions, sintering powders, spreadingMANUFACTURING EXAMPLES Example 1 25.8 g of l,Z-naphthylideneimidazolone(0.14 mol; melting point 347C) together with 388.5 g of epichlorohydrin(4.2 mols) and 0.5 g of tetramethylammonium chloride are stirred for 110 minutes at 1 15 l 18C. A clear, dark solution thereby results. Asample taken from the batch and freed of volatile constituents (aboveall epichlorohydrin, dichlorohydrin and the like) then shows an epoxidecontent of 3.61 equivalents/kg (53.6 percent of theory). An azeotropiccirculatory distillation is established by applying vacuum (-90 mm Hg)at an external temperature of 140 148C in such a way that at atemperature of the reaction mixture of 59-6lC a vigorous distillationtakes place. 246 g of 50 percent strength aqueous sodium hydroxidesolution (0.308 mol) are then added dropwise over the course of minuteswith vigorous stirring; at the same time the water present in thereaction mixture is continuously removed azeotropically, and separatedoff.

Thereafter, distillation is continued for 30 minutes under the indicatedconditions in order to remove the last remnants of water from the batch.The sodium chloride produced in the reaction is removed by filtration;the residue is washed with a little epichlorohydrin and the combinedepichlorohydrin solutions are extracted by shaking with 50 ml of waterto remove salt and remnants of alkali. The organic phase is concentratedat 60C under a waterpump vacuum and is then dried to constant weight atl00C/0.2 mm Hg. 38.5 g (93 percent of theory) of a dark, viscous resinare obtained. The epoxide content is 5.88 equivalents/kg (87 percent oftheory). The product can be recrystallised by recrystallisation fromacetone in the ratio of 1:1. A purified product is obtained in the formof a yellowish crystal powder which melts at l l7l 19C and has anepoxide content of 6.68 equivalents/kg. In agreement with the formulagiven below, the microanalysis gives the following values:

Found: Calculated:

68.75% C 68.90% C 5.46% H 5.447: H 9.54% N 9.45% N Example 2 Analogouslyto Example 1, 118.5 g of 5- methylbenzimidazolone (0.8 mol) are reactedwith 1,480 g of epichlorohydrin (16.0 mols), using 1.5 g oftetramethylammonium chloride; the dehydrohalogenation is carried outwith 140.8 g of 50 percent strength aqueous sodium hydroxide solutionaccording to Example 1. The mixture is worked up as described Found:Calculated:

64.56% C 64.6071 C 6.21% H 6.20% H 18.4571 0 18.4471 0 10.78% N 10.76% NAccordingly, the new diglycidyl compound corresponds to the followingstructure:

Example 3 The following substances are reacted as described in Example1: 48.6 g of 5,-dimethylbenzimidazolone (0.3 mol), 555 g ofepichlorohydrin (6.0 mols), 0.5 g of tetramethylammonium chloride and52.8 g of 50 percent strength aqueous sodium hydroxide solution (0.66mol). The conduct of the reaction, working up and isolation of thesubstances take place analogously to Example 1, and g (theory 82.3 g) ofbrown crystals containing 6.74 epoxide equivalents/kg (92.5 percent oftheory), and having a melting point of l20133C and a total chlorinecontent of 3.3 percent are obtained as the crude product. Purificationis effected by recrystallisation from acetone in the ratio of 1:3 andcolourless crystals containing 7.05 epoxide equivalents/kg (96.8 percentof theory) and having a melting point of l40-144C are obtained in 56.2percent yield.

Accordingly, the new compound corresponds to the following structure:

Example 4 Following Example 1, 33.7 g of 5- chlorobenzimidazolidone (0.2mol) are reacted with 555 g of epichlorohydrin (6.0 mols) with the aidof 1 g of tetramethylammonium chloride. The dehydrohalogenation takesplace as described above with 35.2 g of 50 percent strength aqueoussodium hydroxide solution (0.44 mol). After the customary working up, 55g of a brown crystal mass (98 percent of theory) containing 6.53 epoxideequivalents per kilogram (91.5 percent of theory) are obtained, thechlorine content being 13.82 percent (theory 12.63 percent).

For purification, the material is recrystallised from acetone in theratio of 1:7. Practically colourless crystals melting at 135-139C areobtained; the epoxide content is 7.13 equivalents/kg (100 percent oftheory). Analysis by combustion shows:

Use Example 100 g of the purified diglycidyl compound manufacturedaccording to Example 3 (7.64 epoxide equivalents/kg) are mixed with l l1.8 g of hexahydrophthalic anhydride at 80C and the mixture isde-aerated and poured into an aluminium casting mould prewarmed to 80C.Curing takes place in 5 hours at 80C 2 hours at lC 20 hours at 150C.Clear, transparent mouldings having the following properties areobtained:

1. A DIGLYCIDYLBENZIMIDAZOLONE COMPOUND OF THE FORMULA